In 1836, King Otto I commissioned the Bavarian architect Friedrich von Gärtner, recommended by his father, Ludwig I of Bavaria, to design a palace that would house not only the royal family but also the ministerial cabinet.

The building served as the official royal residence until 1910, when George I chose to move to the Crown Prince's Palace nearby, which now houses the presidency of the Hellenic Republic.

The final selection of the site for the construction of the old palace was made by Gärtner himself at the end of 1835, after rejecting the proposals of Kleanthis, Schaubert, Klenze, and Schinkel, who had suggested locations in Omonoia, Kerameikos, and the Acropolis, respectively.

Thus, Gärtner was instructed to draft the building’s plans, a task he accomplished in a short time during his brief stay in Athens (from December 1835 to March 1836), a feat made possible only by his considerable expertise.

From his office in Munich, Gärtner completed the detailed studies, producing a total of 247 designs related solely to the Athens palace building.

These designs are now part of Munich’s large Moniger collection, while a small number have been donated to the Parliament Museum, demonstrating the care put into every detail.

Once the walls were completed in November 1840, Gärtner returned to Athens to oversee the continuation of the construction and the interior decoration, bringing with him renowned historical painters of the time, Johann Schraudolph, Ulrich Halbreiter, and Josef Kranzburger.

After a three-month stay, Gärtner returned to Munich, leaving the engineer Riedel in charge, who successfully completed the building in 1847.

On 3 September of the same year, General Dimitrios Kallergis, with his men and a large part of the population, presented themselves at the windows of the sovereign to compel him to grant a constitution to the Kingdom.

At the same time, George I had two summer residences built: the Tatoi Palace, about twenty kilometers north of Athens, and the Mon Repos villa on the island of Corfu.

The palace was then used for many different purposes: housing a variety of government and public services in the 1920s, functioning as a makeshift hospital during World War II, a refugee shelter for Greek refugees from the Greco-Turkish War (1919–1922) in 1922, a museum with the personal effects of King George I (now part of the collection of the National Historical Museum), and other uses.

In 2003, new statues were unveiled to honor two prominent Prime Ministers of the country, Charilaos Trikoupis and Eleftherios Venizelos, further enhancing the republican image of the Palace.

The central wing, with a double-pitched tiled roof, extends 0.58 meters beyond the eastern and western facades, creating two pediments at the edges.

As Oswald Hederer notes in his book Friedrich von Gaertner: "...when King Ludwig (of Bavaria) crossed out all the decorative elements of the facades with a red pencil, Gärtner is said to have remarked, somewhat indignantly, 'Well, now, Your Majesty, it looks like a barracks!'"